2-cyano-2, 3-diacetoxy butanes



Patented July 12, 1949 assignors to Wingfoot Corporation,

2,476,026 PATENT OFFICE Akron,

Ohio, a corporation of Delaware No Drawing.

Original application January 18,

1940, Serial No; 314,462. Divided and this application March 19, 1943,Serial No. 479,764

Claims.

This invention relates to new compounds containing a nitrile radical andto methods of preparing the same. More particularly, it relates tointermediates which may be used in the prepara tion of compounds ofunsaturated nature intended for use in the preparation of polymerizedcompositions.

In the preparation of polymerized compositions various unsaturatedsubstances have been polymerized, either alone or in admixture withother unsaturated compounds. To the available monomers have recentlybeen added the 2-cyano 1,3-butadienes, which may be prepared from2-cyano diacetoxy butanes.

It is, accordingly, an object of this invention to make available theZ-cyano diacetoxy butanes. Other objects are also attained in thepractice of the invention, as will appear hereinafter.

The method of preparation of the 2-cyano diacetoxy butanes, in general,consists in treating an acetoxy butanone or a hydroxy butanone withhydrogen cyanide to convert the ketone to a cyanhydrin. Thereafter, thiscyanhydrin is reacted with acetic anhydride which eifects theintroduction of one or two acetoxy groups, the product being, in eithercase, a Z-cyano diacetoxy butane.

To illustrate the process, the following examples are given, but will beunderstood that the same are merely by way of illustration, and that theinvention is not limited thereto.

Example 1 Into 246 grams of 3-acetoxy-2-butanone there was passed 51.5grams of hydrogen cyanide, the temperature being maintained between 40and 50 C. during the operation. The mixture, con taining a nitrilecompound, was then acetylated with 212 grams of acetic anhydridecontaining 5 grams of sulphuric acid. The reaction mixture wasfractionated under reduced pressure to give Z-cyano 2,3-diacetoxy butanehaving a boiling point of 124-138 C./8 mm. The density was d3c=1.0905,and the index of refraction was n =1.4282. The compound has notpreviously been described.

The reactions involved in the foregoing example may be represented bythe following equations:

OH 0A0 CH-CH; HOAc Ac OAc Example 2 In another preparation, 408 grams ofl-hydroxy Z-methyI-B-butanone was treated with 108 grams of hydrogencyanide and then with 897 grams of acetic anhydride in the mannerdescribed above, to yield 2-methyl 3-cyano 1,3-diacetoxy butane. Thisintermediate compound, which is believed to be new, had a boilin pointof 148-158 C./11 mm. The density Was d3o=1.0865, and the index ofrefraction was n =1.4402.

The conditions given in the foregoing examples can be varied, of course,the temperature at which the hydrogen cyanide gas is passed in beingpreferably in the neighborhood of -60 C. and that of acetylationsomewhat higher, from 100 to 120 C. Distillation of the 2-oyanodiacetoxy butane should be carried out under reduced pressure, apressure corresponding to 10 to 60 mm. of mercury being foundsatisfactory.

From the foregoing, it will be apparent that the present inventionembraces within its scope a class of new compounds, namely, the 2-cyanodiacetoxy butanes, which includes, among others,

2-cyano 2,3-diacetoxy butane; Z-methyl 3-cyano 1,3-diacetoxy butane;2-cyano 3-methyl 2,3-diacetoxy butane; 3-cyano 1,3-diacetoxy butane;Z-ethyl 3-cyano 1,3-diacetoxy butane; 2"-pheny1 S-cyano 1,3-diacetoxybutane; and 4-phenyl 2-cyano 2,3-diacetoxy butane. The invention alsoincludes methods of preparing the 2-cyano diacetoxy butanes.

This application is a division of our copendmg application, Serial No,314,462, filed January 18, 1940, now matured into Patent No. 2,328,890.

While there have been described above certain preferred embodiments ofthe invention, the lat ter is not limited thereto, but only by the appended claims wherein it is intended to set forth all features ofpatentable novelty residin in the invention.

We claim:

1. The 2-cyanc 2,3-diacetoxy butanes.

2. 2-cyano-2,3-diacetoxy butane.

3. A method of preparing cyano diacetoxy butanes which comprisestreating one of the group consisting of hydroxy butancnes and acetoxybutancnes with hydrogen cyanide and then acetylating the nitrile soformed.

4. A method of preparing 2-cyano diacetoxy butanes which comprisestreating one of the group consisting of hydroxy butancnes and acetoxybutancnes with hydrogen cyanide and then acetylating with aceticanhydride the nitrile so formed.

5. A method of preparing a diacetoxy-cyanobutane which comprises mixinga hydroXy-substituted butanone with gaseous hydrogen cyanide to form adihydroxy-cyano-butane, mixing said 3 4 product with acetic anhydride inthe presence of UNITED STATES PATENTS sulfuric acid, and separating theresulting Number Name Date dlacetOXY'cyam-butane' 2 2,208,328 LichtyJuly 16, 1940 2,265,814 Ritchie Dec. 9, 1941 ALBERT CLIFFORD 2,301,131Lichty Nov,3,1942

JOHN R. LONG.

' OTHER REFERENCES REFERENCES CITED Lichtenstern, Beilstein (4th ed),vol. III, The following referenlces are of record in the 403. (Copy 1nScientific Library.) file of this patent: V Koch et a1, Beilstein (4thed.), Handbuch der Organischen Chemie (1921), vol. III, p. 401.

(Copy in Div. 6.)

